N-mercapto ureas



United States Patent O V N- MERCAPTO UREAS Hugo Malz,L'everkusen-Wiesdorf, Giinter Oertel,

Cologne-Flittard, and Hans Holtschmidt, Cologne- Stamrnheim, Germany,assignors to Farbenfab'riken Bayer Aktiengesellschaft, Leverkusen,Germany, a German corporation No Drawing. Filed Nov. 14, 1962, Ser. No.237,713 Claims priority, applica't i on Germany, Nov. 16, 1961,

F 35,370 v 4 Claims. '(Cl. 260-552) The present invention relates 'toand has 'as its object new'and tedhnically interesting sulphenylatedureas and thioureas as well as a process for the production thereof.More specifically, this invention is concerned with compounds of thegeneral formula:

In this formula, R stands for an optionally "substituted aliphatic oraromatic hydrocarbon radical, R and R; denote hydrogen or optionallysubstituted indentic'al or different hydrocarbon radicals and R standsfor an optionally substituted hydrocarbon radical or for the residue:

For the production of these new sulphenylated (thio)- ureas, molarmixtures of the above mentioned reaction components areheatedoptionally. in the presence of inert solvents or diluents such as,for example, --ligroin, petroleum ether-or aromatic hydroc'arbonstotemperatures of about-40m C. In general, a Weakly exothermic reactionthen commences. -1n'other cases, it might be necessary to heat thereaction mixture at to about C. for some time (about /2 to 1 hour) inorder to complete the reaction. According to the solvents or diluentsused and according to the nature of the reaction components used, thesulphenylated ,(=thio)-ureas obtained reci itate from the reactionmixture in the form of colourless 'to yellow crystals or oils, or can beobtained by evaporation of the solution in almost quantitative yields.They are soluble, without decomposition, in many organic solvents andare completely stable, even on prolonged storage. The sulphenamides-anddiamino-monosulphides used as intermediate products in the inventivereaction are known from the literature.

The new compounds obtainable according to the present invention aresuitable as active substances for plant protection agents, especially asherbicides and may be used for the control of undesired plant growth andthe destruction of weeds. In -the latter respect thetinventive compoundsmay be applied to the same way and in the same quantities as the knownherbicide N-(p-chlorophenyl)-N', N-dimethylurea, is i.e. in the form of'dusts in combination with borax, quartz sand, pumice grit or similarmaterials; the active ingredient may be used in concen- 'trationsbetween 1. 5 to 10kg. per ha. of soil to be treated depending on theheight and dense occurrence of the weed to be killed.

The inventive compounds mentioned in the following table havebeen-tested in respect of their herbicidal ac- -tivit'y.

Aqueous dilutions of'these compounds have been prepared by mixing theact-ive ingredient with acetone as an auxiliary solvent, adding theretoa commercial emulsifier and diluting this premixture i at last withwater to the desired concentration as indicated above. Th herbicidalactivity of the compounds can be seen from the following table. Thesetests employing aqueous solutions of the compounds were carried out 24-hours after sowing (preemergence and post-emergence respectively) andthe evaluation occurred three weeksxlater. The arabic numerals-given inthe table are evaluation results, 0 meaning no effect and 5 meaningatotal effect (plants not germinati-ng or dying after germinating).

Quantity used 7 m Compound Application Millet Beet Oats Cotton Wheat-Mus- Toma- Beans turd v toes Per- Kgjha. 2 cent H NSNCN HPost-emergence" 0. 4 5 0 0 0 0 4 0 0 Pres-emergence- 40 4 3 0 0 0 3 Si(C H NSNCN(C H )g Postemergenceu 0. 4' 5' 2 2 0 2 5' 4 2 1Pris-emergence- 40 1 4 5 1 2 '5 Quantity used in Compound ApplicationMillet Beet Oats Cotton Wheat: Mus- Toma- Beans tard toes Per- KgJha.cent Cl Cl i Cl S -NC N( C H 2 Post-emergence 0. 4 5 4 2 2 4-5 4 2 I x lPre-emergence- 4O 3 1 0 1 4-5 C1 C1 i r a: 1111;; t a a 2 a -2 a gFire-emergence- 4 5 1 0 2 5 1 1 -s-N-oN o2n5)2 Postemergcnoe 0.4 3 1 1 0o 1 1 2 Fi e-emergence- 40 4 5 2 1 1 3 CH i @s-N-c-MQER 5 4-5 1 1 2 3 12 Post-emergence. 5 4-5 0 0 1 2 0 1 4-5 4-5 0 O 0 2 0 0 Pre-emergence 25 l 0 1 4 The following examples are given for the purpose ofillus-Example 2 trating the invention in more detail.

Example 1 0 Ns-N- JN 0 O ll O -N O 13 g. of dimorpholine sulphide areintroduced at C. into a solution of 8 g. of phenyl isocyanate in 20 ml.of ligroin. An exothermic reaction occurs, with the separation ofcolourless crystals which, upon prolonged stirring at 50 C., dissolve.The clear yellow solution is evaporated in a vacuum, whereupon 20 g. ofthe above compound remain in the residue in the form of a pale brown oilwhich, upon prolonged standing, solidifies to a waxlike mass.

In the same manner as described above there are obtained the followingcornopunds:

48.8 g. of dimorpholine sulphide are introduced at 50- 70 C. into asolution of 27 g. of phenyl mustard oil in 50 50 ml. of ligroin. Anexothermic reaction occurs. The temperature of the mixture is maintainedin the stated range by cooling the reaction vessel with ice water.

After the introduction of the sulphide, there results a clear solutionfrom which, upon further heating at 60 C., the reaction productseparates in the course of an hour in the form of yellow crystals. Aftercooling to room temperature, the crystals are filtered oil with suctionand dried in a vacuum. There are obtained g. (90% of the theoreticalyield) of the above compound in the form 60 of yellow crystals ofmelting point 126 C.

Formula Physical properties CgH5 B.P.O.1: 0-- Yellow oil.

40.8 parts of dimorpholine sulphide are introduced, with cooling, at 70C into 30 g of methyl mustard oil In analogous manner there are obtainedthe following compounds:

Physical properties Yellow oil.

Red-brown 011 Yellow crystals.

. Yellow oil.

7 Light yellow-oil.

Formula i H N S%I C-N H Emm l8 3 70 After the very vigorous reaction hassubsided, the reaction p mixture 15 heated at 80 C in a vacuum for 1hour In l| the residue there remain 56 g. (100% of the theoreticalamount) of the above compound in the form of a clear L (1E1 75 yellowoil.

Under reaction conditions analogous to that described above there areobtained the following compounds:

8 into a solution of 17.6 g. of bis-diethylamino-monosulphide in 80 ml.of light benzine. The reaction mixture Formula Physical properties S llH NSNCN H Yellow oil.

i CH:) NS-1| ICN -CH2 Yellow, viscous oil.

CH l (CzH5)zNSl?'CN(C2H )g B.P. 0.1: 90 C Yellow oil.

Example 4 20 'g. of dipiperidino-monosulphide are dissolved in 75 ml. ofwashing benzine and, after the addition of 13.5 g. of phenyl mustard oilthe mixture is heated for about one hour at 60-70 C. The yellow clearsolution is then evaporated in a vacuum, whereby a pale yellow clear oilis obtained as residue, which, after a few minutes, solidifies ascrystals. After recrystallisation from a little petroleum ether, thereare obtained pale yellow crystals with a melting point of 70 C. Crudeyield: 32 g.=95% of the theoretical. Calc.: for C1'7H25N3S2CZ 60.9%, H:7.5%, N: v

S: 19.1% Found: C: 60.8%, H: 7.7%, N: 12.3%, S: 19.1%

Mice only show symptoms after oral application of 1,000 mg. of thecompound per kg. of animal, whilst after subcutanal application of 100mg. per kg. of mouse only symptoms of poisoning occurred, but nomortality.

Example 5 (Q Qf l Q QX Example 6 13.5 g. of phenyl mustard oil,dissolved in about 80 ml. of light benzine, are added dropwise, withstirring,

thereby warms up to about 30 C. and there is obtained a green-yellowsolution which is stirred for about a further /z hour at about 60 C.Subsequently, the reaction mixture is evaporated and there are obtained28 g. of a golden yellow viscous oil which cannot be distilled withoutdecomposition.

Example 7 Cl S-IIT N(CH3)2 l I C1 01 Calc.: for C H N S Cl C: 39.1%; H:2.39%, N:

6.1%,S: 13.9%,Cl: 38.6%

Found: C: 38.8%, H: 2.39%, N: 6.1%, S:

1,000 mg. of the compound per kg. of animal do not effect any symptom iforally administered to mice.

1 1 We claim: 1. The compound of the formula 2. The compound of theformula 3. The compound of the formula 4. A compound having the formulain which R is a member-selected fromwther group consisting of a loweralkyl up to 4 carbon atoms, phenyl, halogen substituted phenyl,nitro-substituted phenyl, lower alkoxy substituted phenyl and loweralkyl mereapto substituted phenyl, the lower alkoxy and lower alkylmercapto in each case having up to 4 carbon atoms; wherein R and R aremembers selected from the group consisting of a hydrogen, lower alkyl,phenyl and benzyl; R is a member selected from the group consisting of alower alkyl having up to 4 carbon atoms, phenyl, halogen substitutedphenyl; and wherein X stands for a member selected from the groupconsisting of oxygen and sulfur.

References Cited by the Examiner UNITED STATES PATENTS 2,343,538 3/1944Ebelke 260-247.1 XR 3,084,192 4/1963 Srnothers 260553 1 3,115,52412/1963 Shapiro et al 260553 3,119,682 1/1964 Martin 71-26 3 3,126,2723/1964 Fisher et a1. 71-2.7

:NICHOLAS s. RIZZO, Primary Examiner.

4. A COMPOUND HAVING THE FORMULA